Four alkyl lactates and alkyl lactate acrylates having methyl, ethyl, propyl, and butyl as alkyl moiety were synthesized by azeotropic distillation. Their formation was confirmed by Fourier transform infrared (FTIR), mass, 1H nuclear magnetic resonance (NMR) and proton decoupled 13C NMR spectroscopic techniques. Solution polymerization was carried out for these alkyl lactate acrylates and the formed homopolymers were characterized by FTIR, 1H NMR, proton decoupled 13C NMR spectroscopic, and gel permeation chromatographic techniques. Shear thinning behavior was observed for all the polymers. Wide angle X-ray Diffraction studies showed that the polymers were amorphous in nature and also exhibited odd-even effect among alkyl lactate groups with respect to average molecular interchain spacing. Depending on the length of the alkyl lactate groups, relative humidity and time, the hydrophilicity of the polymers decreased with increase in the length of the alkyl lactate group among the odd and even series. Among the studied polymers, poly(ethyl lactate acrylate) may have the potential for hydrogel applications, due to its highly hydrophilic nature. Tg decreased with increase in length of alkyl lactate groups. Trend observed on the thermal stabilities of poly(alkyl lactate acrylate)s could be explained on the basis of average molecular interchain spacing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40962.